Aza-crown macrocycles as chiral solvating agents for mandelic acid derivatives.

A series of new chiral macrocycles containing the trans-1,2-diaminocyclohexane (DACH) subunit and arene- and oligoethylene glycol-derived spacers has been prepared in enantiomerically pure form. Four of the macrocycles have been characterized by X-ray crystallography, which reveals a consistent mode of intramolecular N-H···N hydrogen bonding and conformational variations about the N-benzylic bonds. Most of the macrocycles were found to differentiate the enantiomers of mandelic acid (MA) by (1)H NMR spectroscopy in CDCl(3); within the series of macrocycles tested, enantiodiscrimination was promoted by (i) a meta-linkage geometry about the arene spacer, (ii) the presence of naphthalene- rather than phenylene-derived arene spacers, and (iii) increasing length of the oligoethylene glycol bridge.

Thermoresponsive dynamers: thermally induced, reversible chain elongation of amphiphilic poly(acylhydrazones).

A nanostructured poly(acylhydrazone), which is reversibly formed in acidic aqueous solution from di(aldehyde) and di(acylhydrazine) monomers with appended hexaglyme groups, was found to display lower critical solution (LCS) behavior. Remarkably, under acidic conditions in which polymerization is reversible, large and reversible molecular weight (M(w)) increases were observed in response to elevated temperatures, both below and above the LCS temperature. No variation in M(w) was evident under neutral and alkaline conditions, in which the acylhydrazone condensation is essentially irreversible.

Using enantioselective indicator displacement assays to determine the enantiomeric excess of alpha-amino acids.

Enantioselective indicator displacement assays (eIDAs) were used for the determination of enantiomeric excess (ee) of alpha-amino acids as an alternative to the labor-intensive technique of chromatography. In this study, eIDAs were implemented by the use of two chiral receptors [(Cu(II)(1)](2+), [Cu(II)(2)](2+)) in conjunction with the indicator chrome azurol S. The two receptors were able to enantioselectively discriminate 13 of the 17 analyzed alpha-amino acids.

Pattern-based discrimination of enantiomeric and structurally similar amino acids: an optical mimic of the mammalian taste response.

This manuscript describes an optical enantioselective pattern-based sensing array. A differential array of enantioselective indicator displacement assays was constructed and used to demonstrate simultaneous discrimination of enantiomeric and structurally similar alpha-amino acids. Interpretation of the output patterns by principle component analysis leads to the separation of enantio- and chemoselective information along orthogonal variance axes when chiral receptors of opposite enantiomeric preference are included.